Interpolymers of fumaric esters and a chlorinated alkene



Patented Feb. 21, I950 2,498,084 INTERPGkYMERS F FUMARIC ESTERS CHLO =1 .lw ATED ALKENE Jerome G. Kndema, 3n, Passaic, N; 1., and Robert H. Snyder, Chicago, BL, assignors to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Application April 19, 1946, Serial No. 663,616

I Our invention comprises a method for pre- 1 paring a new class of unsaturated polymeric materials of relatively low molecular weight which Bare soluble in a variety of organic liquids. but

which are convertible to insoluble, infusible resins in the presence of heat and/or catalysts,

by further polymerization or by copolymerization with reactive compounds containing an ethylenic linkage.

More particularly, our invention relates to unsaturated, polymeric materials derived from a monomeric allylic fumarate and a monomeric allylic halide. These new binary copolymcrs contain halogen which improves their resistance to burning and thus renders them of use in the preparation of flame-proofing compositions for coating and impregnation purposes. When the allylic halide employed contains a second halogen atom the interpolymers with the allylic fumarates are completely self-extinguishin in the well-known A. S. T. M. test.

Prior workers in this art of polymerizing allylic fumarates have encountered diiliculty in controlling the polymerization of these allylic fumarates so as to obtain soluble, fusible polymers. Various devices for increasing the yield of the soluble, fusible polymer have been suggested such as carrying out polymerization at elevated temperatures, preferably at about 180 C. or higher. However, since the rate of the polymerization is enormously accelerated at these temperatures, the control of the reaction'becomes difiicult, particularly in a reaction vessel of industrial size, and premature insolubilization of the reaction mixture becomes increasingly diflicult to avoid. Also, heretofore it has been known to obtain high yields of soluble, fusible polyallylic fumarates by polymerizing the furnarate in an inert solvent and keeping the concentration of the monomeric allylic fumarate below 40% by weight. However, the rate of polymerization in such case tends to decrease in dilute solutions, the conversion of monomer to polymer is still comparatively inefiicient, and the solvent-increases the material cost which necessitates additional time and labor for its removal from the reaction prodnot, and lowers the production capacity of the reaction vessel.

We have now unexpectedly found that polymerizing an allylic fumarate ,inthe presence of a. suflicient quantity, that is, at least (based on the weight of the fumarat-e) of a monomeric halogeno-alkene having at least 3 :arbon atoms, preferably those of the formula JnHzn-rCh (where n is an integer greater than 3 and :x: is 1 or 2) by heating the mixture, pref- :rabiy at temperatures below 120 C., and in the -n'osence of a conventional peroxidic catalyst, :ives high yields of soluble, fusible interpolymers. the reaction temperatures employed preferably 6 Claims. (Cl. 260-785) range from about 25 C. to about (1., although higher temperatures may be used if desired. Examples of suitable catalysts among others are acetyl peroxide, benzoyl peroxide, acetyl benzoyl peroxide, succinyl peroxide and tertiary-butyl hydrogen peroxide, etc.

The course of the polymerization can be followed by observing the increase in the viscosity of the reaction mixture and when the copolymerization has proceeded to the desired extent the reaction is halted by cooling. The resulting interpolymer can be recovered from the reaction mixture by distilling out any unreacted starting materials or by extracting them with a solvent in which the polymer is insoluble such as n-hexane; The interpolymer can be further purified by dissolving it in a solvent for the polymer such as acetone and precipitating with a non-solvent such as n-hexane.

The concentration of the monomeric .allylic fumarate in the reaction mixture does not have to be kept below 40% in fact, the reaction can be carried out in the absence of any solvent other than the copolymerizable monomers themselves. Since our interpolymers are soluble in allylic halides we prefer to carry out the interpolymerizations in the presence of an excess of the allylic halide, for the resulting mobile, free-flowing solutions are easily handled in transfer, mixing, storage and other mechanical operations to which the solid interpolymers themselves may be less amenable. The allylic halide in our invention may thus serve not only as a copolymerizable monomer but also as a cheap volatile solvent which because it shows little tendency to homopolymerize under these conditions can be easily removed from the reaction mixture by distillation and recovered for use in subsequent copolymerizations.

That our new products are true interpolymers of an allylic fumarate and an allylic halide is indicated by elementary analyses and other specific tests. They contain attached to the polymer chain halcmethyl groups derived from the interpolymerized allylic halide molecules which render the copolymer capable of being modified by treatment with appropriate reagents, which replace the halogen with various groups such as hydroxyl, mercapto, alkoxy, alkenoxy, acyloxy, cyano, etc. Metathetical reactions can also be carried out with corresponding polyfunctional reagents such as the sodium salts of polycarboxylic acids, glycols, etc. B .such reactions ourynew polymers can be converted into other modified polymers having desirable properties.

The allylic fumarates which we have found to be most suitable in the practice of our invention are diallyl fumarate, dimethallyl fumarate and di-(2-chloroallyl) fumarate, while the preferred allylic halides are the 2-alkenyl halides having chloride, 2-chloroallyl chloride, 2-(chloromethyl) allyl chloride, 3-chloroallyl chloride, etc. For cases where the resin must be completely self-extinguishing, we have found the copolymers of an allylic iumarate with 2=chloroallyl chloride and with 2-chloromethyl allyl chloride to be most suitable.

Other halogenated alkenes (i. a, other than oneness linkage such as methyl acrylate, diallyl iumarate, vinyl acetate, aliylacrylate, etc. The resulting solutions can be totally copolymerized to insoluble, infusible products, if need be, without leaving any solvent to be evaporated. Even at high solids content many of the solutions are still quite fluid and can be employed as coating materials by spraying, brushing, and dipping. They can also be employed in casting, laminating and impregnating operations, particularly where arti-- cles capable of being preformed and then "set or cured in a final shape are desired. Curing,

the allyiic type) containing more than two cartemperatures oi. 60 (L-120 C. are suitable. bo a m 8. so 1 D D isccrotyl Chlo- The following examples disclose our invention ride, etc, can also be employed in our invention, i more t il; ,11 parts being by weight; although in general they are somewhat inferior l to the above mentioned allylic halides in repress- LE 1 ing the gelation of the polymerizing reaction To illustrate our discovery that by copolymerimixtures. However, a mixture of isomeric dization of an allylic fumarate with an allylic 1'18."- chlorobdtenes (B. Pt. Bil-135 C. at 760 mm.; id the gelation of the reaction mixture is re- N =l.4739) obtained as a by-product in the pressed, a series of copolymerizations or various chlorination of isobutylene, has proven to be as mixtures of an allylic fumarate and allylic hacfiicacious as many of the simple allyiic halides lides are carried out at 60 C. in the presence of in carrying out our invention. The principal benzoyl peroxide catalyst. component of this mixture is believed to be an copolymerizations of allylic" (i. e., 2-alkenyl) allylic-type chloride of the formula filifinargteas with 2-chloropropene, and with the dic oro u one mixture previously described, are CH2 C(CH2CD CHZCI also included, to demonstrate that not only the The relative proportions of the allylic furnarate allylic halides but other halogenated olefines and the allylic halide may be varied over a concontaining more than two carbon atoms are opsiderable range, including 10% to 500% of the erative in our invention. The copolymerizations halide on the weight of furnarate, depending upon are halted at the point of incipient gelation by the physical properties and the amount of haiocooling and adding a trace of hydroquinone as a gen desired to be present in the polymeric prodpolymerization inhibitor. The copolymers are not. Copolymerization of the allylic fumarate then isolated by pouring the reaction mixtures with as little as 10% of an allylic halide (based into ligroin and the precipitated polymers are on the weight of the allylic fumarate) retards further purified by dissolving them in acetone the gelation of the reaction mixture during the and precipitating with ligroin. After drying to early stage of the polymerization and insures the constant weight, the conversion of monomers to production of a soluble, fusible product. The polym r i d t mi i h case higher the amount of the allylic halide present, The data are summarized in Table I showing the higher is the proportion of the monomeric the weights of the copolymerizable monomers, allylic fumarate which can be converted to the $5 the peroxide catalyst and the purified products. polymeric stage without insolubilization. together with the times elapsed at the point of The copolymers can be cast or molded in a incipient gelation, (except those marked with an known manner to form rods, blocks or sheets. asterisk which did not gel). For purposes They can also be dissolved in an appropriate of comparison only. the allylic fumarates are solvent and employed as lacquers or as an imalso polymerized under identical conditions but i pregnating and waterproofing composition. in the absence of allylic halides. It is apparent I Application of heat to compositions containing that by copolymerization of the allylic fumarate 1 our unsaturated interpolymers, particularly in with sufllcient amounts of allylic halides, high 1 the presence of catalysts, induces further polyyields of soluble, fusible copolymers are obtained. merization and the resulting cross-linked prod- Comparison of 1-1 with 1-2 and 1-34 with L35 nets are quite indiiferent to attack by solvents. clearly shows the eflect of even small amounts Suitable dyes, pigments, fillers, and plasticizers of the allylic halide in increasing the amount of can be incorporated with our interpolymers at the conversion of the monomeric allylic fumarate to Y soluble, fusible stage prior to final cure. the soluble, fusible polymeric form. 1-8 and I-16 Our unsaturated interpolymers can be dissolved illustrate the variation in the yield of soluble, in many organic solvents, particularly in copolyfusible interpolymer which is achieved by vary- Q merizable'compounds containing an ethylenic ing the copolymerizable allylic halide. Table I Dian 1 Dimethmg: Allyl Meth- 2-Ohioroaohlom- Dichlor- 20mm Baum Time to I Fummite Fu z ate fm 51 d? oiii t r l de (ll l i de 01 5 1 31 iit fife Pmpan" mug; 31 Yield 1 1.0 4.15 0. 2 1.5 3.75 20. a 3.7 4.75 as. 4 7.3 7.00 47. a 0.3 11. 7s 72 0 11.2 18.25 70. 7 18.6 74.0 121. s 1.5 0.0 33. 0 1.9 21.0 M. 10.. 24 32.0 75. 11 1 8.1 33.0 07.

aeeacea Fifty-six parts of dimethallyl fumarate are heated with. 90.5 parts of methallyl chloride and 3.03 parts of benzoyl peroxide for 31 hours at 90 C. The product is isolated and purified as in pretermiuing the viscosities of these solutions, they are admixed with benzoyl peroxide and polymerized by heating at elevated temperatures. The resultingcastings are clear, insoluble in organic solvents'and substantially infusible. They will not support combustion even after 30 seconds exf;

vious examples, and yields 51 parts of polymeric posure' to a flame. The data are summarized in solid. Table III. I p

Table III Copolymerizable Monomer, parts fiig Inter- Viscosity Peroxide Hard- 1 [1181' r I pa rts Methyl Allyl B-chlor- Diallyl Pam 1188 Acry- Acryeth l Fums- 60 0. 100 C.

late late Acry ate rate 3.0 135 45 7 M-l b. 8.0 0.135 is M-103 0.5 0.135 45 M-00 a..-" 4.0 0.12 41 a M-72 14.0 0.12 Y 41 L-77 Analysis-Found: C, 60.68%; H, 7.40% CI. EXAMPLE 8 12.3% Iodine number 101.0.

The analysis corresponds to a copolymer derived from approximately 68.7% by weight of dimethallyl fumarate and 31.3% of methallyl chloride. 7

A solution of 10 parts of the interpolymer in 4.5 parts of methyl acrylate has a viscosity of 4.5 poise at C. Thes'olution is admixed with 0.18 part of benzpyl' 'peroxide and heated ingaj mold for 18 hours'at 60 C.'and then for 4hoursat 100 .C. The resulting transparent casting is i'ndifierent to attack by organic solvents and has 75.0% of the monomeric diallyl fumarate to the polymeric form. Another sample of the copolymer is prepared by heating a mixture of 9.8 parts of diallyl fumarate, 22.2 parts of 2-chloroallyl chloride and 0.605 part of benzoyl peroxide at 60 0. for 102 hours. Thirty and sixteen-hundredthsparts of the crude reaction mixture are evacuated at 1 mm. and 25 C. until 3.42 parts of unreacted starting materials have "been removed. Ten parts of monomeric styrene are then added and the evacuation is continued until the total weight of the residue is 79.7 parts. This solution of the diallyl fumarate-2-chloroallyl chloride copolymer in monomeric styrene is admixed with 0.6 part of benzoyl peroxide and heated in a mold for 16 hours at 70 C. The clear casting has a Rockwell hardness of L-1l2 and M-102, is unattacked by acetone, and will not support combustion.

EXAMPLE 7 various copclymerizable monomers and after defrom approximately 76% .35 a Rockwell hardness of M-82. A similar casting having a Rockwell hardness of M402 is secured One hundred parts of diallyl fumarate are and 6.2 parts of benzoyl peroxide for 9 hours at, 60 C. to yield 63 parts of'solid purified polymer. uiiralysis -Found-z C', 57.85%; H, 6.35%; CI,

0. The analysis indicates a copolymer derived by weight of diallyl fumarate and 24% of allyl chloride.

EXAMPLE 9 A mixture of 19.6 parts'of diallyl fumarate, 112.5 parts of a mixture of isomeric dichlorobutenes and 2.42 parts of benzoyl peroxide is heated at 60 C. for 145 hours, and after purification as in he preceding examples, 59.2 parts of polymeric solid are secured.

Analysis-Found: C, 47.16%; 37.56%; Iodine number 41.7.

The analysis corresponds to a copolymer containing approximately 34.0% by weight of diallyl fumarate and 66% of one or both of the isomeric dichlorobutenesz' 'I'en parts of the copolymer are dissolved in 4.5 parts of'monomeric diallyl fumarate together with 0.09" part of benzoyl peroxide and the mixture is heated in a mold for 24 hours at 60 C., then for 5.5 hours at C., and finally for an additional 15 hours at 60 C. to yield a clear casting which is unattacked by acetone and has a Rockwell hardnessof L-95.

EXAMPLE 10 A-mixture of 10.6 parts of di-(Z-chloroallyl) H, 5.24 Cl,

' fumarate, 17.8 parts of 2-chloroa1ly1 chloride and V 0.48 part of benzoyl peroxide is heated for 51 hours at 60 C., and after the usual purification, 15.5 parts of colorless polymeric solid are obtained.

-..Analysls-Found: C, 39.88%; H, 3.79%; 01,

The analysis corresponds to a copolymer containing approximately 57% by weight of di-(2- chloroallyl) fumarate and 43% of z-chloroallyl chloride.

Three and five-tenths parts of the copolymer are dissolved in 1.5 parts of monomeric styrene together with 0.045 part of benzoyl peroxide and the mixture is heated in a mold for 46 hours at 60 C. yielding a clear solvent-resistant casting which does not support combustion.

A casting is made in an analogous manner employing monomeric diallyl fumarate in place 9 of styrene. The product is flame-resistant and insoluble in acetone.

The soluble 2-chloroal1yl chloride-diallyl fumarate is especially useful; it has a low, indefinite softening point, i. e., it sinters to a glossy mass even at ordinary room temperatures; at 70 C. it is like very heavy molasses, and at 120 C. it is like glycerine; it is soluble in acetone, chloroform, vinyl acetate, methyl acrylate, allyl alcohol, diallyl fumarate, styrene, etc.; it has considerable unsaturation, thereby enabling it to react readily with polymerizable unsaturated monomers.

While we have shown and described various embodiments of the invention, it is to be understood that the invention is susceptible to those modifications which appear within the spirit of the invention and the scope of the appended claims.

Having thus described our invention, what we claim and desire to protect by Letters Patent is:

1. A soluble unsaturated binary copolymer of a di-2-alkenyl fumarate selected from the class consisting of diallyl fumarate, dimethallyl fumarate, and di(2-chloroallyl) fumarate and a chlorinated-alkene having from three to four carbon atoms prepared from a mix in which the said alkene ranges from -500% by weight based on the weight of the fumarate.

2. A soluble unsaturated binary copolymer of a di-2-alkenyl fumarate selected from the class consisting of diallyl fumarate, dimethallyl fumarate, and di(2-chloroally1) fumarate and a. chlo- 'rinated-alkene having the formula C1LH21::C1:

where n is an integer of 3 to 4; a: is an integer of from 1 to 2 prepared from a mix in which the said alkene ranges from 10-500% by weight based on the weight of the fumarate.

3. A soluble unsaturated binary copolymer of a di-2-alkenyl fumarate selected from the class consisting of diallyl fumarate, dimethallyl fumarate, and di(2-chloroallyl) fumarate and a chlorinated-alkene having the formula CnIhn-xClr where n is an integer of 3 to 4; a: is 2 prepared from a mix in which the said alkene ranges from 10-500% by weight based on the weight of the fumarate.

4. A soluble unsaturated binary copolymer of a di-2-alkenyl fumarate selected from the class consisting of diallyl fumarate, dimethally1 fumarate and di(2-chloroallyl) fumarate and 2-chloroallyl chloride prepared from a mix in which the said chloride ranges from 10-500% by weight based on the weight of the fumarate.

5. An organic solvent solution of a soluble unsaturated copolymer of a di-2-alkenyl fumarate selected from the class consisting of diallyl fumarate, dimethallyl fumarate, and di(2-chloroally1) fumarate and a chlorinated-alkene having from three to four carbonatoms said copolymer being prepared from a mix in which the said alkene ranges from 10-500% by weight based on the weight of the fumarate, in which the organic solvent contains an ethylenic linkage and is substantially completely polymerizable with the said soluble binary copolymer whereby to produce a solution which can be totally copolymerized to an insoluble infusible product.

6. A method which comprises polymerizing with heat and in the presence of a peroxidic polymerization catalyst a di-2-alkenyl fumarate selected from the class consisting of diallyl fumarate, dimethallyl fumarate, and di(2-chloroallyl) fumarate with a chlorinated-alkene having at least three carbon atoms, the polymerization being carried out at a temperature in the range from about 25 C. to about C. and halting the polymerization before the gel point, to form a soluble fusible unsaturated binary copolymer of said monomers the proportion of the said alkene ranging from 10-500% by weight based on the weight of the fumarate.

JEROME G. KUDERNA, JR.

ROBERT H. SNYDER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,392,756 Mighton Jan. 8, 1946 2,419,2 1 Kenyon et al Apr. 22, 1947 2,431,374 DAlelio Nov. 25, 1947 2,433,616 Marple et a1 Dec. 30, 1947 

1. A SOLUBLE UNSATURED BINARY COPOLYMER OF A DI-2-ALKENYL FUMARATE SELECTED FROM THE CLASS CONSISTING OF DIALLYL FUMARATE, DIMETHALLYL FUMARATE, AND DI(2-CHLOROALLY) FUMARATE AND A CHLORINATED-ALKENE HAVING FROM THREE TO FOUR CARBON ATOMS PREPARED FROM A MIX IN WHICH THE SAID ALKENE RANGES FROM 10-500% BY WEIGHT BASED ON THE WEIGHT OF THE FUMRATE. 